KR101436146B1 - Catalyst system for producing acrolein from glycerol and the method of producing acrolein by using said catalyst system - Google Patents

Abstract

The present invention relates to a catalyst system comprising indium phosphate as a main component used for producing acrolein from glycerol and a method for producing acrolein using the same, wherein the catalyst system of the present invention comprises a catalyst component represented by the following general formula 1:
[Formula 1]
In _x P _y O _a
(here,
The molar ratio of In: P is selected from x: y = 1: 1 to 3;
a corresponds to the oxidation state thereof with the amount of oxygen bound to the other element).

Description

TECHNICAL FIELD The present invention relates to a catalyst system used for producing acrolein from glycerol, and a method for producing acrolein using the same. BACKGROUND ART [0002]

The present invention relates to a novel catalyst system used to prepare acrolein from glycerol.

The present invention also relates to a process for preparing acrolein from glycerol using a novel catalyst system.

Acrolein is one of the unsaturated aldehydes and is a coloring liquid of the formula CH ₂ = CHCHO. It is easily oxidized in the air and preserved for a long time to polymerize into a dendritic material, which is used as a raw material for organic synthesis.

The production of such acrolein has been employed as a general industrial production method in which propylene is used as a starting material and a gas phase oxidation is carried out using a catalyst. However, recently, there has been a demand for a method of manufacturing fuels or organic products from biomass resources without depending on fossil resources, and a method for producing acrolein from glycerol has been continuously studied.

As a method for producing acrolein from glycerol, iron phosphate is generally used to produce acrolein. Such methods are disclosed in JP-A-2010-0059891, JP-A-2007-0104413, JP-A- (Catalysis Today 157 (2010), p351-358), which is incorporated by reference herein in its entirety, such as those disclosed in U.S. Patent Application Publication No. 2006-011724, U.S. Patent Application Publication No. 2011/0136954 and the like, Journal of Molecular Catalysis A Chemical 309 And Applied Catalysis A: General Vol. 378 (2010), p11-18].

Specifically, Japanese Patent Application Laid-Open No. 2010-0059891 discloses a method for producing acrolein by dehydration of glycerol under a nitrogen atmosphere using a catalyst system of iron phosphate including oxygen, iron and phosphorus.

In addition, Japanese Patent Application Laid-Open No. 2007-0104413 discloses a method for producing acrolein by dehydration of glycerol using ZrO ₂ , or TiO ₂ and SnO ₂ at 40 ° C in Nafion / SiO ₂ at 280 ° C have.

Japanese Patent Application Laid-Open No. 6-211724 discloses a method of obtaining acrolein from glycerol by a dehydration reaction through a reaction in which a glycerin / water mixture is contacted with a solid catalyst in a liquid phase or a vapor phase.

In addition, U.S. Patent Publication No. 2011/0136954 discloses a method for producing acrolein by dehydrating glycerol from an aqueous glycerol solution under an acidic catalyst to prepare a mixture of acrolein and water, Lt; / RTI >

In addition, a support of 100 wt% of PO ₄ and 15 wt% of H ₃ PO ₄ was supported by x-Al ₂ O ₃ and TiO ₂ -Antas in Journal of Molecular Catalysis A Chemical 309 (2009), p 71-78, Discloses a process for obtaining acrolein from glycerin.

However, even with the above-mentioned method, hydropropylene, propaldehyde, acetaldehyde, acetone and the like are still produced as by-products together with acrolein, and the catalyst used also has a problem in that the selectivity of acrolein is remarkably deteriorated Lt; / RTI >

Therefore, there is still a need to develop a catalyst system in which production of byproducts is suppressed to further improve the conversion and selectivity of the desired acrolein, and the acrolein conversion and selectivity are maintained even after repeated use, and a method for producing acrolein.

An object of the present invention is to provide a catalyst system comprising indium phosphate as a main component which improves selectivity and conversion of acrolein from glycerol and maintains selectivity and conversion ratio even in repeated use.

The present invention also provides a method for producing acrolein from glycerol using the catalyst system.

In order to achieve the above object, the present invention provides a catalyst system comprising indium phosphate as a main component as described below, and a method for producing acrolein from glycerol using the catalyst system.

(1) A catalyst system used for producing acrolein from glycerol, comprising: a catalyst system comprising a catalyst component represented by the following general formula 1:

[Formula 1]

In _x P _y O _a

(Wherein the molar ratio of In: P is selected from x: y = 1: 1 to 3; a is the amount of oxygen bound to the other element and corresponds to its oxidation state).

(2) a catalyst system used for producing acrolein from glycerol, comprising a catalyst component represented by the following general formula 2:

[Formula 2]

In _x M _z P _y O _a

Wherein M represents at least one metal selected from the group consisting of an alkali metal, an alkaline earth metal, Fe, Nb, Cu and Co; a molar ratio of In: M is selected from x: z = 1: 0.1 to 10; In + M): The molar ratio of P is selected from (x + z): y = 1: 1 to 3; a is the amount of oxygen bound to the other element and corresponds to its oxidation state.

(3) A process for producing acrolein from glycerol, which process is carried out in the presence of a catalyst system comprising a catalyst component represented by the general formula (1) or (2).

(4) A process for producing acrolein from glycerol, which process is carried out in a reactor containing hydrogen gas in the presence of a catalyst system comprising a catalyst component represented by the general formula (1) or (2).

(5) The method according to (1) or (2), wherein the catalyst system comprising the catalyst component is repeatedly used at least twice.

The use of the indium phosphate catalyst system of the present invention improves the selectivity and conversion of acrolein from glycerol and maintains selectivity and conversion of acrolein even during prolonged or repeated use.

The use of the indium phosphate catalyst system of the present invention improves the selectivity and conversion of acrolein from glycerol and maintains selectivity and conversion of acrolein even during prolonged or repeated use.

Hereinafter, the present invention will be described in more detail.

The catalyst system used in the present invention is a catalyst system used when dehydrating glycerol to produce acrolein, and includes a catalyst component containing indium phosphate as a main component.

The catalyst component used in the present invention is preferably a catalyst component represented by the following general formula (1).

[Formula 1]

In _x P _y O _a

here,

The molar ratio of In: P is selected from x: y = 1: 1 to 3; a corresponds to the oxidation state thereof with the amount of oxygen bound to the other element, preferably a has a value of 1 to 12. [

The catalyst component used in the present invention may further contain at least one metal M selected from the group consisting of alkali metals, alkaline earth metals, Fe, Nb, Cu and Co in addition to indium and phosphorus as essential components. The alkali metals include Li, Na, K, Rb, Cs, and Fr, and the alkaline earth metals include Be, Mg, Ca, Sr, Ba, and Ra.

The catalyst component containing two or more metal components is preferably a catalyst component represented by the following general formula (2).

[Formula 2]

In _x M _z P _y O _a

here,

M represents at least one metal selected from the group consisting of alkali metals, alkaline earth metals, Fe, Nb, Cu and Co; The molar ratio of In: M is selected from x: z = 1: 0.1 to 10; (In + M): the molar ratio of P (x + z): y = 1: 1 to 3; a corresponds to the oxidation state thereof with the amount of oxygen bound to the other element, preferably a has a value of 1 to 12. [

 The catalyst system of the present invention may further include a support. Preferable supports include silica, alumina, titanium oxide, silicon carbide, silicate, borate, carbonate and the like. A more preferred support is alumina. The support may be used alone or in combination of two or more, and the catalyst component is supported on the support, so that the catalyst component can be utilized more advantageously.

The catalyst component is preferably 30 to 50 wt% of the total weight of the catalyst system, and the support is preferably 50 to 70 wt% of the total weight of the catalyst system.

The shape of the catalyst system is not particularly limited, and may be amorphous granules or powder. However, for gas phase reaction, a shaping aid may be used in combination with a spherical body, a pellet, a cylindrical body, a rod or the like. The size of the formed catalyst system is preferably 10 to 500 mesh, more preferably 20 to 50 mesh.

The production method of the catalyst system of the present invention is not particularly limited. It is possible to produce the catalyst system of the present invention by the conventional method described in the prior art mentioned in the background art.

The present invention provides a process for producing acrolein from glycerol using a catalyst system comprising a catalyst component represented by the general formula (1) or (2).

The method of the present invention is particularly preferably carried out in a reactor comprising a hydrogen gas. In the case of the production in a reactor containing hydrogen gas, the yield of glycerol conversion and acrolein selectivity are excellent by reducing the production of byproducts as compared with the case of production in a nitrogen atmosphere. Further, since the carbon deposition does not occur and the catalytic activity is maintained, the catalyst life also becomes longer. However, if necessary, the reactor may further include at least one gas selected from the group consisting of an oxygen gas, a nitrogen gas, a carbon dioxide gas, and an inert gas.

The process according to the invention can be carried out in a gaseous or liquid phase, more preferably applied in a gaseous phase. When the reaction is carried out in the gas phase, there are various reactors such as stationary phase, fluidized bed, circulating fluidized bed, mobile phase and the like.

The reaction in the liquid phase can be carried out in a typical liquid phase reactor for solid catalysts. Since the difference between the boiling point (290 DEG C) of glycerol and the boiling point (53 DEG C) of acrolein is large, it is preferable to operate at a relatively low temperature which enables continuous distillation of the produced acrolein.

The temperature in the reactor in the gas phase reaction and the liquid phase reaction is 100 to 500 ° C, but the temperature in the reactor is more preferably 150 to 300 ° C. At high pressure, vaporized glycerol may be re-liquefied, and carbon precipitation may be promoted, resulting in a shortened catalyst life.

It is preferred that the glycerol in the reaction be provided in the form of an aqueous glycerol solution. The glycerol content in the glycerol aqueous solution is preferably in the range of 5 to 90 wt%, more preferably in the range of 10 to 50 wt%. When the concentration of glycerol is too high, there is a problem that glycerol ether is produced or generated, unsaturated aldehyde or unsaturated carboxylic acid reacts with glycerol, and it is not preferable because a large amount of energy is required to vaporize glycerol.

The catalyst system used after producing acrolein according to the present invention can be regenerated and used.

In the method for producing acrolein according to the present invention, the production conditions such as temperature, pressure, and time in the reactor were obtained experimentally through repeated experiments. Therefore, problems due to the upper limit and lower limit of each condition were not considered, It can be understood that the conditions which are considered optimal for the purpose of the present invention are described.

Hereinafter, the present invention will be described in more detail with reference to examples. However, the following examples are intended to illustrate the present invention, and the present invention is not limited by the following examples, but may be variously modified and changed.

[Example]

Indium phosphate Catalytic  Produce

First, 15 g of? -Alumina was dispersed in deionized water. Next, a solution (solution A) in which 25.37 g of In (NO ₃ ) _{3 3} H ₂ O was dissolved in deionized water and 85% H ₃ PO ₄ (Solution B) was prepared. Then, solution B was added to the alumina-dispersed solution, followed by coprecipitation, followed by stirring for 1 hour. Then, the solution A was further added to the stirred solution, and most of the distilled water in the solution was evaporated while stirring for 1 to 2 hours. It was again dried with a microwave and then dried at 120 ° C for 12 hours. The dried cake was pulverized and formed into tablets. The obtained molded body was separated into a size of 20 to 40 mesh, and then calcined at 400 DEG C for 5 hours in an air atmosphere to prepare an indium phosphate catalyst system.

Various catalyst systems were prepared by adjusting the ratio of In or by adding Fe and / or Li components under the same conditions and methods as described above.

 Production Example 1 _{50% InPO 4 / α-alumina} (In / P molar ratio = 1: 1.7)  Production Example 2 50% InFePO ₄ / α-alumina (In / Fe / P molar ratio = 0.1: 0.9: 1.84)  Production Example 3 _{50% InFePO 4 / α-alumina} (In / Fe / P molar ratio of 0.2: 0.8: 1.84)  Production Example 4 50% InFePO ₄ / α-alumina (In / Fe / P molar ratio = 0.4: 0.6: 1.84)  Production Example 6 50% LiInFePO ₄ / α-alumina (Li / In / Fe / P molar ratio = 0.05: 0.2: 0.8: 1.84)

Example  One

₄ g of the catalyst system of InPO ₄ / α-Alumina (In / P molar ratio = 1: 1.7) as the catalyst system of Preparation Example 1 was charged in a 1 / 2˝ tubular reactor and reacted at 400 ° C. under a hydrogen atmosphere of 5%. Thereafter, a continuous reaction was carried out while supplying a glycerol aqueous solution of 30 wt% at a temperature of 250 to 300 ° C and normal pressure together with nitrogen (600 ml / hr).

The product was quantitatively analyzed by gas chromatography. The conversion (%) of glycerol and the selectivity (%) of the products (acrolein and acetol) were calculated by the following formula (1) or (2).

[Equation 1]

Conversion rate of glycerol (%) = (mole of glycerol reacted / mole of glycerol supplied) X100

&Quot; (2) "

Product selectivity (%) = (moles of product / mole of glycerol reacted) X100

Examples 2 to 6

Acrolein was prepared from glycerol in the same manner as described in Example 1, except that the catalyst systems of Production Examples 2 to 6 were used, and conversion of glycerol (%) over time and selectivity of products (acrolein and acetol) (%) Was calculated.

Conversion (%) and selectivity (%) results of acrolein

The conversion (%) of acrolein and the selectivity (%) of acrolein and acetol obtained according to the methods of Examples 1 to 6 are summarized in Table 2 below.

catalyst
Furtherance reaction
gas Reaction time
(Hr) Reaction temperature
(° C) Conversion Rate (%) Selectivity (%) Acrolein Acetol Example 1 Production Example 1 Hydrogen 2 280 100 88.1 8.8 24 300 100 84.1 11.6 Example 2 Production Example 2 Hydrogen 2 280 100 88.1 2.6 24 300 99.4 83.5 12.5 50 300 97.9 82.8 12.4 Example 3 Production Example 3 Hydrogen 2 280 86.6 94.2 0 24 300 90.7 79.0 11.3 50 300 100 85.2 11.8 Example 4 Production Example 4 Hydrogen 2 280 100 89.6 4.9 24 300 100 86.4 9.4 50 300 100 87.2 9.9 Example 5 Production Example 5 Hydrogen 2 280 100 94.5 1.2 24 300 100 83.9 10.2

From Table 2 above, it can be seen that acrolein can be obtained from glycerol with high conversion (%) and selectivity (%) when using the catalyst system of the present invention.

Also, it can be seen that the conversion (%) and selectivity (%) of acrolein are maintained even if the reaction time is prolonged.

Comparative Examples 1 to 3

Acrolein was prepared from glycerol using the catalyst systems of Production Examples 1 to 3 in the same manner as in the methods described in Examples 1 to 3 except that the catalyst was prepared in a nitrogen atmosphere instead of a hydrogen atmosphere and the conversion of glycerol %) And selectivity (%) of the products (acrolein and acetol) were calculated.

Conversion (%) and selectivity (%) results of acrolein

The conversion (%) of acrolein and the selectivity (%) of acrolein and acetol obtained according to the methods of Comparative Examples 1 to 3 are summarized in Table 3 below.

catalyst
Furtherance reaction
gas Reaction time (Hr) Reaction temperature
(° C) Conversion Rate (%) Selectivity (%) Acrolein Acetol Comparative Example 1 Production Example 1 nitrogen 2 280 77.4 63.9 22.1 50 300 96.0 68.4 21.5 Comparative Example 2 Production Example 2 nitrogen 2 280 100 87.9 0 50 280 95.5 64.4 13.7

Comparing Tables 2 and 3, it can be seen that higher acrolein conversion (%) and selectivity (%) are obtained when acrolein is produced from glycerol in a hydrogen atmosphere compared to nitrogen atmosphere even when the same catalyst system is used.

Claims (9)

A catalyst system used for producing acrolein from glycerol, comprising: a catalyst system comprising a catalyst component represented by the following general formula:
[Formula 1]
In _x P _y O _a
(here,
x: y = 1: 1 to 3;
a corresponds to the oxidation state thereof with the amount of oxygen bound to the other element). The method according to claim 1,
Wherein the catalyst component further comprises a metal M and is represented by the following general formula 2:
[Formula 2]
In _x M _z P _y O _a
(here,
M represents at least one metal selected from the group consisting of alkali metals, alkaline earth metals, Fe, Nb, Cu and Co;
x: z = 1: 0.1 to 10;
(x + z): y = 1: 1 to 3;
a corresponds to the oxidation state thereof with the amount of oxygen bound to the other element). 3. The method according to claim 1 or 2,
Wherein the catalyst system further comprises at least one support selected from the group consisting of silica, alumina, titanium oxide, silicon carbide, silicate, borate and carbonate. A process for producing acrolein from glycerol, using the catalyst system of claim 1 or 2. 5. The method of claim 4,
Characterized in that the process is carried out in a reactor comprising hydrogen gas. 6. The method of claim 5,
Wherein the reactor further comprises at least one gas selected from the group consisting of steam, oxygen gas, nitrogen gas, carbon dioxide gas and inert gas. 6. The method of claim 5,
Wherein the temperature in the reactor is between 100 and < RTI ID = 0.0 > 500 C. < / RTI > 5. The method of claim 4,
Characterized in that the process is carried out in a liquid phase or a gas phase. 5. The method of claim 4,
Wherein the catalyst system is repeatedly used at least twice.